Inkjet ink containing amine-modified silicone

Abstract

An inkjet ink comprising (A) a terpene phenolic resin, (B) a solvent system comprising (B1) ethanol and (B2) a co-solvent, and (C) an amine-modified silicone comprising a silicone backbone (main chain) and one or more organic amine side chains attached to the silicone backbone. The inkjet ink is characterized by an extended decap time and excellent adhesion to a variety of substrates. A printed article comprising the inkjet ink in a dry form and a method for forming a printed image using a thermal inkjet printhead are also provided.

Description

[Technical Field]

[0001] Cross-reference to related applications This application claims priority to PCT application PCT / US2022 / 051379, filed November 30, 2022. [Background technology]

[0002] [Field of the Invention] The present invention relates to a solvent-based inkjet ink, particularly an inkjet ink formulated with a (B) solvent system comprising (A) a terpene phenolic resin, (B1) ethanol, and (B2) a co-solvent, and (C) an amine-modified silicone comprising a silicone backbone (main chain) and one or more organic amine side chains attached to the silicone backbone.

[0003] [Background explanation] The "Background" discussion provided herein is intended to generally describe the contents of the present disclosure. The work of the presently named inventors, to the extent that it is described in this Background section, as well as aspects of this specification that may not qualify as prior art at the time of filing, are not admitted expressly or impliedly as prior art against the present invention.

[0004] Thermal inkjet (TIJ) printing is a desirable technology for printing, coding, and marking because it offers higher print resolution at lower cost than competing technologies in the field, such as continuous inkjet (CIJ) methods. In the thermal inkjet printing process, a print cartridge contains a series of small chambers, each containing a heater, which generate ink droplets from the thermal evaporation of the ink solvent. In the jetting process, a resistor is rapidly heated to create a vapor bubble (hence the term "bubble jet"), which subsequently expels a droplet from an orifice. This process is extremely efficient and repeatable, and modern TIJ printheads for industrial graphics applications can produce uniform droplets of 4 pL or less in volume at frequencies of 36 kHz or greater.

[0005] However, industrial marking and coding regularly requires printing critical information, such as personal information, labels, codes, dates (e.g., expiration dates), and traceability information (e.g., production lot), on substrates with complex surfaces, e.g., radial, curved, sawtooth, corrugated, grooved, and / or lipped, or on a variety of different substrates, e.g., porous and non-porous substrates, or substrates formed from materials with different physicochemical properties. These different substrate characteristics can result in different ink adhesion characteristics. If the ink cannot properly adhere to the substrate, the resulting printed image will have poor image quality. Poor image quality is unacceptable for many applications, especially when marking or coding critical information. The addition of resins to inks has been proposed as a means of improving adhesion.

[0006] However, thermal inkjet printing can suffer from poor reliability after a period of disuse in resin-added systems. For example, some inkjet inks have short decap times, and solvent loss from prolonged exposure to air in an uncapped printhead can lead to clogged / clogging of printhead nozzles, resulting in unreliable ink jetting and degraded image quality over time.

[0007] Solvent-based inkjet inks have been produced using specific combinations of binder resins, modified silicones, and volatile organic solvents or solvent mixtures containing ethanol, and colorants. For example, WO2021 / 176086 discloses inkjet inks containing polyether-modified silicones and ethanol. However, this document does not include amine-modified silicones. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] International Publication No. 2021 / 176086 Brochure Summary of the Invention [Problem to be solved by the invention]

[0009] [Summary of the Invention] In view of the above, there is a need for inkjet inks that have extended decap times and strong adhesion to multiple substrates. It is therefore an object of the present invention to provide novel ink-jet inks that meet these criteria. It is another object of the present disclosure to provide novel printed materials that include the dried form of the ink-jet ink. It is another object of the present disclosure to provide a novel method for forming a printed image on a substrate by applying and drying an inkjet ink onto the substrate. [Means for solving the problem]

[0010] These and other objects, which will become apparent during the course of the detailed description below, have been achieved through the inventors' discovery that a combination of a terpene phenolic resin, a solvent system comprising ethanol and a co-solvent, and an amine-modified silicone provides an inkjet ink characterized by extended decap times and excellent adhesion to substrates.

[0011] Thus, the present invention provides the following: (1) (A) Terpene phenolic resin; (B) a solvent system comprising (B1) ethanol and (B2) a co-solvent; and (C) An inkjet ink containing an amine-modified silicone, The inkjet ink, wherein the amine-modified silicone (C) comprises a silicone skeleton (main chain) and one or more organic amine side chains bonded to the silicone skeleton.

[0012] (2) The terpene phenol resin (A) is a copolymer containing a monoterpene segment and a phenolic segment containing a phenolic compound, The inkjet ink according to (1), wherein the phenolic segment is bonded to the monoterpene segment at at least one position selected from the group consisting of an ortho position relative to the phenolic hydroxyl group and a para position relative to the phenolic hydroxyl group.

[0013] (3) the monoterpene segment is at least one bicyclic monoterpene selected from the group consisting of 3-carene, α-pinene, β-pinene, and camphene; The inkjet ink according to (2), wherein the phenolic compound is phenol.

[0014] (4) The ink-jet ink according to any one of (1) to (3), wherein the terpene phenol resin (A) has a hydroxyl value of 10 to 75 mgKOH / g.

[0015] (5) The ink-jet ink according to any one of (1) to (4), wherein the terpene phenol resin (A) is present in an amount of 0.1 to 10% by weight based on the total weight of the ink-jet ink.

[0016] (6) The ink-jet ink according to any one of (1) to (5), wherein the (B2) co-solvent is at least one selected from the group consisting of n-propanol, methyl ethyl ketone, ethyl acetate, propylene glycol monomethyl ether, and 1,3-dioxolane.

[0017] (7) The inkjet ink according to any one of (1) to (6), wherein the weight ratio of (B1) ethanol to (B2) co-solvent ((B1):(B2)) is 1:1 to 25:1.

[0018] (8) The ink-jet ink according to any one of (1) to (7), wherein the organic amine side chain is at least one selected from the group consisting of monoamines containing a primary amine and diamines containing a primary amine and a secondary amine.

[0019] (9) The viscosity of the amine-modified silicone (C) at 25°C is 25 to 250 mm2 The inkjet ink of any one of (1) to (8), wherein the ink composition is / s.

[0020] (10) The ink-jet ink according to any one of (1) to (9), wherein the amine functional group equivalent of the amine-modified silicone is 350 to 11,000 g / mol.

[0021] (11) The ink-jet ink according to any one of (1) to (10), wherein the amine-modified silicone is present in an amount of 0.1 to 10% by weight.

[0022] (12) The inkjet ink of claim 1, which is substantially free of polyether-containing surfactants.

[0023] (13) The inkjet ink according to any one of (1) to (12), further comprising (D) an alkanolamine.

[0024] (14) The ink-jet ink of (13), wherein the alkanolamine (D) is present in an amount of 0.01 to 5% by weight, based on the total weight of the ink-jet ink.

[0025] (15) The ink-jet ink according to (13), wherein the alkanolamine (D) is at least one selected from the group consisting of ethanolamine, propanolamine, isopropanolamine, diethanolamine, and triethanolamine.

[0026] (16) The inkjet ink according to any one of (1) to (15), further comprising (E) a colorant.

[0027] (17) The inkjet ink according to (16), wherein the colorant (E) is a metal complex azo dye.

[0028] (18) A printed matter comprising a substrate and a dried form of the inkjet ink of any one of (1) to (17) disposed on the substrate.

[0029] (19) A method for forming a printed image on a substrate, comprising: The method includes applying any one of the inkjet inks (1) to (17) onto the substrate using a thermal inkjet print head; and drying the inkjet ink; The method wherein the substrate is substantially free of amine-modified silicone.

[0030] The foregoing paragraphs have been provided by way of a general introduction and are not intended to limit the scope of the claims that follow. The described embodiments, together with further advantages, will be best understood by reference to the following detailed description when considered in conjunction with the accompanying drawings, in which: [Brief explanation of the drawings]

[0031] [Figure 1] Figure 1 shows the "good" rating (clearly legible, sharp, clear image), "acceptable" rating (readable and mostly clear, but with some haze and slight loss of edge clarity), and "poor" rating (unreadable, poor clarity, poor clarity) for printing ink on an alphanumeric string. [Figure 2] Figure 2 shows the peel tape test adhesion ratings for the printed images: "good" (little ink on the tape, no change in the print), "acceptable" (heavy ink on the tape, noticeable change in the print, e.g., hatching or fading), and "poor" (heavy ink on the tape, significant degradation in print quality, e.g., hatching or fading). DETAILED DESCRIPTION OF THE INVENTION

[0032] [Detailed Description of the Invention] In the following description, it is to be understood that other embodiments may be utilized and structural and operational changes may be made without departing from the scope of the present embodiments disclosed herein.

[0033] The phrase "substantially free," unless otherwise specified, means that the amount of a particular component in the inkjet ink is less than 1 wt. %, preferably less than 0.5 wt. %, more preferably less than 0.1 wt. %, even more preferably less than 0.05 wt. %, and even more preferably 0 wt. %, based on the total weight of the inkjet ink.

[0034] As used herein, the term "optional" or "optionally" means that the subsequently described event(s) may or may not occur, or that the subsequently described ingredient(s) may or may not be present (e.g., 0 wt %).

[0035] The term "alkyl," as used herein, unless otherwise specified, refers to a straight-chain, branched, or cyclic aliphatic fragment having at least 1, preferably at least 2, preferably at least 3, preferably at least 4 carbon atoms, and up to 22, preferably up to 20, preferably up to 18, preferably up to 12, preferably up to 8 carbon atoms. Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, isopentyl, neopentyl, hexyl, isohexyl, 3-methylpentyl, 2-dimethylbutyl, 2,3-dimethylbutyl, lauryl, myristyl, cetyl, stearyl, and the like, including, but not limited to, Guerbet-type alkyl groups (e.g., 2-methylpentyl, 2-ethylhexyl, 2-propylheptyl, 2-butyloctyl, 2-pentylnonyl, 2-hexyldecyl, 2-heptylundecyl, 2-octyldodecyl, 2-nonyltridecyl, 2-decyltetradecyl, and 2-undecylpentadecyl). Cycloalkyl is a type of cyclized alkyl group. Exemplary cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, and adamantyl.

[0036] As used herein, the term "fatty" refers to compounds that have a long-chain (straight-chain) hydrophobic moiety composed of hydrogen and generally 8 to 22 carbon atoms, and may be fully saturated or partially unsaturated.

[0037] As used herein, the term "aryl" refers to aromatic groups containing only carbon in the aromatic ring(s), for example, phenyl, biphenyl, naphthyl, anthracenyl, and the like.

[0038] The term "arylalkyl," as used herein, refers to a straight-chain, branched, or cyclic alkyl moiety (as defined above) substituted by an aryl group (as defined above), which itself may be optionally substituted with an alkyl group, examples of which include, but are not limited to, benzyl, phenethyl, 3-phenylpropyl, 2-phenylpropyl, 1-phenylpropyl, 4-phenylbutyl, 3-phenylbutyl, 2-phenylbutyl, 2-methylbenzyl, 3-methylbenzyl, 4-methylbenzyl, 2,4-dimethylbenzyl, 2-(4-ethylphenyl)ethyl, 3-(3-propylphenyl)propyl, and the like.

[0039] As used herein, the term "fatty" refers to compounds that have a long-chain (straight-chain) hydrophobic moiety composed of hydrogen and generally 8 to 22 carbon atoms, and may be fully saturated or partially unsaturated.

[0040] The term "(meth)acrylate" is used herein to refer to both acrylate and methacrylate groups. In other words, the term should be read as if the "meth" is optional. Furthermore, the term "(meth)acrylate" is generally used to refer to both acrylic acid-based compounds and acrylic ester-based compounds.

[0041] Throughout this specification, the term "boiling point" (bp) refers to the boiling point of a liquid measured at sea level atmospheric pressure (i.e., 760 mmHg or 1 atmosphere), also referred to as the normal boiling point, unless otherwise specified.

[0042] The term "decap behavior" herein refers to the ability of an inkjet ink to easily eject from a printhead when exposed to air for an extended period of time. The "decap time" of an inkjet ink is measured as the amount of time an inkjet printhead can be left uncapped before the printer's nozzles no longer fire properly, potentially due to clogging or plugging upon resuming printing. Generally, nozzle(s) can become clogged (i.e., impeded or slowed) or clogged (i.e., blocked, substantially or completely closed) by viscous plugs that form within the nozzle(s) as a result of solvent loss, ink crusting, and / or kogation of various ink components within and / or around any nozzle. When a nozzle becomes clogged, ink droplets ejected through the nozzle orifice can be misdirected, adversely affecting print quality. When an orifice becomes clogged, it becomes substantially or completely blocked. As a result of a clogged nozzle, ink droplets cannot pass through the affected nozzle. Thus, the measure of a nozzle's failure to fire is any misdirection of ink through the nozzle orifice, or complete blockage, which can be measured by visually inspecting the printed image.

[0043] The term "halftone dot" refers to a print defect characterized by an incompatibility between an inkjet ink and the substrate surface, causing the ink film to peel off from parts of the substrate. Halftone dots often cause an "orange peel" or "pinhole" effect in the image.

[0044] [Inkjet ink] The present disclosure relates to inkjet inks that have suitable physical and chemical stability at both ambient and printhead operating temperatures, jet reliably, exhibit good adhesion to porous and non-porous substrates, and dry quickly after application onto a substrate while providing extended decap times.

[0045] Inkjet inks of the present disclosure generally include the following components: (A) a terpene phenolic resin; (B) a solvent system comprising (B1) ethanol and (B2) a co-solvent; and (C) an amine-modified silicone.

[0046] The inkjet inks of the present disclosure may optionally include one or more of (D) an alkanolamine and (E) a colorant.

[0047] <(A) Resin(s)> In a preferred embodiment, the terpene phenolic resin (A) used in the inkjet ink is a copolymer containing a monoterpene segment and a phenolic compound segment, and the terpene phenolic resin (A) is a copolymer containing a monoterpene segment and a phenolic segment containing a phenolic compound, and the phenolic segment is bonded to the monoterpene segment at at least one position selected from the group consisting of an ortho position relative to the phenolic hydroxyl group and a para position relative to the phenolic hydroxyl group.

[0048] Terpene phenolic resins (A) are copolymerizable reaction products of one or more phenolic compounds and one or more terpenes by alkylation and have been used in inks and adhesives to impart a tackifying effect. As known to those skilled in the art, such resins can be easily obtained by copolymerizing phenol and terpene monomers under the action of a catalyst such as a strong acid, a metal salt with a condensation effect, bleaching earth, or a Friedel-Crafts catalyst (e.g., boron trifluoride). Furthermore, the copolymerizable reaction product may contain other structural units in addition to structural units derived from phenolic compounds and terpenes. That is, terpene phenolic resins (A) contain both units derived from terpene units and units derived from phenolic units.

[0049] The amount of other constituent units other than terpenes and phenols is preferably less than 5% by weight, preferably less than 3% by weight, preferably less than 1% by weight, preferably substantially 0% by weight, preferably 0% by weight, based on the total weight (100% by weight) of the constituent units of the copolymerizable reaction product.

[0050] The terpene phenolic resin (A) used herein can be based on any terpene having at least one olefinic double bond that can be alkylated by a phenolic compound. Terpenes have the basic skeleton (C5H8) p where p is a positive integer that defines the number of isoprene units connected consecutively from head to tail. For example, hemiterpenes (p=1) have a C5H8 backbone, and monoterpenes (p=2) have a C 10 H 16 The skeleton of sesquiterpenes (p=3) is C 15 H 24 The skeleton, etc.

[0051] In some embodiments, the terpene phenolic resin (A) is based on a monoterpene monomer unit. The monoterpene may be a linear monoterpene (e.g., myrcene, ocimene, etc.), a monocyclic monoterpene (e.g., limonene, γ-terpinene, α-phellandrene, β-phellandrene, terpinolene, etc.), or a bicyclic monoterpene (e.g., 3-carene, α-pinene, β-pinene, α-phenchene, camphene, etc.) (including various stereoisomers thereof), or a mixture thereof. In a preferred embodiment, the monoterpene is a bicyclic monoterpene, particularly preferably 3-carene, α-pinene, β-pinene, and camphene, and more preferably α-pinene and / or β-pinene.

[0052] The phenolic compound has at least one hydroxyl group directly bonded to the phenyl ring. Any monohydric or polyhydric phenolic compound is useful for preparing the terpene phenolic resin (A) described herein, provided that the phenolic compound has at least two replaceable hydrogen atoms in the ortho and / or para positions relative to at least one hydroxyl group. That is, the phenolic compound should be capable of being polyalkylated (e.g., bisalkylated) with terpene(s) and therefore should have at least two available ortho / para positions relative to at least one hydroxyl group for alkylation.

[0053] In a preferred embodiment, the phenolic compound is phenol, which is considered to be the parent unsubstituted phenolic compound (i.e., containing one hydroxyl group directly attached to the phenyl ring and no other substituents). Alternatively, the phenolic compound may be substituted at up to three positions in addition to the phenolic hydroxyl group, where one, two, or three of the aromatic hydrogens of the phenol are substituted with an equal number of substituents (each independently, a hydroxyl group; C1-C6). 22 Alkyl groups, preferably C2 to C 18 Alkyl groups, more preferably C3 to C 12 Alkyl groups, even more preferably C4 to C9 alkyl groups, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl; C1 to C 22 Alkoxy group, preferably C2-C 12 It is substituted with an alkoxy group, more preferably a C3-C6 alkoxy group, such as methoxy, ethoxy, and isopropoxy; an aryl group; an arylalkyl group, such as a benzyl group; and a halo group, such as selected from chlorine, bromine, fluorine, and iodine.

[0054] Specific examples of substituted phenol compounds include o-cresol, m-cresol, p-cresol, 2,5-xylenol, 2,3-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, isopropylphenol (e.g., 4-isopropylphenol), tert-butylphenol (e.g., 4-tert-butylphenol), amylphenol (e.g., 4-tert-amylphenol), heptylphenol (e.g., 4-heptylphenol), octylphenol (e.g., o-octylphenol, p-octylphenol), Examples of suitable phenolic compounds include, but are not limited to, phenols such as 4-(2,4-dimethylheptan-3-yl)phenol, decylphenol, dodecylphenol, diphenylolpropane (bisphenol-A), phenylphenols such as 3-phenylphenol, cumylphenol, mequinol, benzyloxyphenol, guaiacol, ethoxyphenols such as 4-ethoxyphenol, and polyhydric phenolic compounds such as resorcinol, pyrogallol, catechol, and p-hydroquinone (including mixtures of two or more of any of the foregoing). Also included are fused-ring phenols such as naphthols (e.g., 1-naphthol, 2-naphthol, etc.) and similar compounds.

[0055] In a preferred embodiment, the terpene phenol resin (A) used in the inkjet ink is a copolymer containing a monoterpene segment, wherein the monoterpene segment is at least one bicyclic monoterpene selected from the group consisting of 3-carene, α-pinene, β-pinene, and camphene; and the phenolic compound is phenol.

[0056] In a more preferred embodiment, the terpene phenol resin (A) used in the inkjet ink is a copolymer containing a monoterpene segment, and the monoterpene segment is at least one bicyclic monoterpene selected from the group consisting of an α-pinene segment and a phenol segment.

[0057] The terpene phenolic resin (A) may be present in the inkjet ink in an amount of at least 0.1 wt.-%, preferably at least 0.2 wt.-%, more preferably at least 0.3 wt.-%, even more preferably at least 0.4 wt.-%, even more preferably at least 0.5 wt.-%, preferably up to 10 wt.-%, more preferably up to 7.5 wt.-%, even more preferably up to 5 wt.-%, even more preferably up to 2.5 wt.-%, even more preferably up to 2.0 wt.-%, even more preferably up to 1.5 wt.-%, even more preferably up to 1 wt.-%, even more preferably up to 0.9% based on the total weight of the inkjet.

[0058] The molecular weight of the terpene phenolic resin (A) can vary depending on the monomers used, the reaction conditions, and many other factors, but typically, the terpene phenolic resin (A) has a weight average molecular weight of at least 200 g / mol, preferably at least 500 g / mol, more preferably at least 600 g / mol, and even more preferably at least 700 g / mol, and up to 3,000 g / mol, preferably up to 2,500 g / mol, more preferably up to 2,000 g / mol, and even more preferably up to 1,500 g / mol.

[0059] The hydroxyl value (OHV) is defined as the number of milligrams of potassium hydroxide required to neutralize the acetic acid incorporated during the acetylation of one gram of a chemical containing free hydroxyl groups. Thus, the OHV, a measure of the relative hydroxyl content of a terpene-phenolic resin (A), is directly correlated with the content of the phenolic compound(s) in the terpene-phenolic resin (A), with a higher OHV indicating a higher incorporation of the phenolic compound (or compounds) into the copolymer (less terpene incorporation). The OHV can be measured according to Japanese Industrial Standard JIS K 0070:1992, "Test Methods for Acid Value, Saponification Value, Ester Value, Iodine Value, Hydroxyl Value, and Unsaponifiable Matter of Chemical Products."

[0060] The hydroxyl value of the terpene phenolic resin (A) used in the disclosed inkjet inks may vary, but typically it is preferred that the hydroxyl value is at least 10 mgKOH / g, preferably at least 12.5 mgKOH / g, preferably at least 15 mgKOH / g, preferably at least 17.5 mgKOH / g, preferably at least 20 mgKOH / g, and preferably up to 75 mgKOH / g, preferably up to 72.5 mgKOH / g, preferably up to 70 mgKOH / g, preferably up to 67.5 mgKOH / g, preferably up to 65 mgKOH / g, preferably up to 62.5 mgKOH / g, more preferably up to 60 mgKOH / g, even more preferably up to 55 mgKOH / g, even more preferably up to 50 mgKOH / g, even more preferably up to 45 mgKOH / g, even more preferably up to 40 mgKOH / g, more preferably up to 35 mgKOH / g. Suitable examples of such terpene phenol resins (A) include, but are not limited to, U130 POLYSTER (OHV=25 mg KOH / g), U115 POLYSTER (OHV=30 mg KOH / g), T160 POLYSTER (OHV=60 mg KOH / g), and T145 POLYSTER (OHV=65 mg KOH / g), available from Yasuhara Chemical Co., Ltd., and DERTOPHENE T (OHV=40 mg KOH / g), DERTOPHENE T160 (OHV=60 mg KOH / g), and DERTOPHENE T105 (OHV=30 mg KOH / g), available from Pinova.

[0061] In addition to the terpene phenol resin (A), the inkjet ink may optionally contain a terpene resin. The terpene resin may contain a small amount of other structural units, other than phenol, as structural units copolymerizable with the terpene(s).

[0062] Such terpene resins may be present in an amount of at least 0.1 wt.%, preferably at least 0.5 wt.%, preferably at least 1 wt.%, more preferably at least 1.5 wt.%, even more preferably at least 2 wt.%, even more preferably at least 2.5 wt.%, and up to 10 wt.%, preferably up to 9 wt.%, preferably up to 8 wt.%, preferably up to 7 wt.%, preferably up to 6 wt.%, more preferably up to 5 wt.%, even more preferably up to 4 wt.%, even more preferably up to 3 wt.%, based on the total weight of said inkjet.

[0063] Terpene resin refers to an oligomer or polymer having at least 95% by weight, preferably at least 96% by weight, more preferably at least 97% by weight, more preferably at least 98% by weight, more preferably at least 99% by weight, even more preferably at least 99.5% by weight, and even more preferably 100% by weight of polymerizable terpene-derived structural units, based on the total structural units (100% by weight) of the terpene resin. Terpene has a basic skeleton (C5H8) p where p is a positive integer representing the number of isoprene units connected consecutively from head to tail. For example, hemiterpenes (p=1) have a C5H8 skeleton, and monoterpenes (p=2) have a C 10 H 16 The skeleton of sesquiterpenes (p=3) is C 15 H 24 It has a skeleton.

[0064] Exemplary terpene resins may be based on monoterpene monomer units. Monoterpenes may include linear monoterpenes (e.g., myrcene, ocimene, etc.), monocyclic monoterpenes (e.g., limonene, γ-terpinene, α-phellandrene, β-phellandrene, terpinolene, etc.), or bicyclic monoterpenes (e.g., 3-carene, α-pinene, β-pinene, α-phenchene, camphene, etc.), and various stereoisomers and mixtures thereof. Monoterpenes may be monocyclic monoterpenes, such as limonene. Monoterpenes may also be bicyclic monoterpenes, such as 3-carene, α-pinene, β-pinene, and camphene.

[0065] As known to those skilled in the art, such terpene resins can be readily obtained, for example, by catalytic polymerization / oligomerization (in solution) of α-pinene monomers, which are typically obtained from the fractional distillation of gum and turpentine sulfate obtained from pine trees such as Pistacia terebinthus, Pinus pinaster, Pinus halepensis, Pinus massoniana, Pinus merkusii, Pinus palustris, Pinus taeda, and Pinus ponderosa.

[0066] The terpene resin may be a homopolymer made from α-pinene, the α-pinene content (units derived from α-pinene) of which, based on the total units of the terpene resin (100% by weight), is at least 95%, preferably at least 96%, preferably at least 97%, preferably at least 98%, preferably at least 99%, more preferably at least 99.5%, even more preferably at least 99.9%, and even more preferably 100% by weight. The terpene resin may be a homopolymer made from β-pinene, the β-pinene content (units derived from β-pinene) of which, based on the total units of the terpene resin (100% by weight), is at least 95%, preferably at least 96%, preferably at least 97%, preferably at least 98%, preferably at least 99%, more preferably at least 99.5%, even more preferably at least 99.9%, and even more preferably 100% by weight.

[0067] Typically, the terpene resins used in inkjet inks have a number average molecular weight (Mn) of at least 330 g / mol, preferably at least 340 g / mol, preferably at least 400 g / mol, preferably at least 450 g / mol, preferably at least 500 g / mol, preferably at least 550 g / mol, preferably at least 600 g / mol, more preferably at least 650 g / mol, even more preferably at least 700 g / mol, even more preferably at least 750 g / mol, and up to 1,500 g / mol, preferably up to 1,300 g / mol, preferably up to 1,100 g / mol, preferably up to 1,000 g / mol, more preferably up to 900 g / mol, even more preferably up to 800 g / mol, even more preferably up to 790 g / mol.

[0068] The terpene resin may be in solid or liquid form at room temperature. If in solid form, the terpene resin used can be classified based on its softening point (SP), for example, according to the ring-and-ball softening point method. The ring-and-ball softening point is defined as the temperature at which a disc of sample held in a horizontal ring is pressed downward a distance of 1 inch (25.4 mm) under the weight of a steel ball as the sample is heated at a predetermined rate in a glycerol bath. For example, the ring-and-ball softening point can be measured according to JIS B7410 (incorporated herein by reference in its entirety): Automatic Ring-and-Ball Softening Point; Tester: Measuring Device: Automatic Ring-and-Ball Softening Point; Testing Machine: ASP-MGK2, manufactured by MEITECH; Heating Rate: 5°C / min; Starting Temperature: 40°C; Measurement Solvent: Glycerol. Terpene resins having a variety of softening points can be used herein, for example, those having a softening point of at least 20°C, preferably at least 22°C, preferably at least 24°C, preferably at least 26°C, preferably at least 28°C, preferably at least 30°C, preferably at least 40°C, preferably at least 50°C, preferably at least 60°C, preferably at least 80°C, preferably at least 100°C, preferably at least 110°C, preferably at least 115°C, more preferably at least 120°C, even more preferably at least 125°C, still more preferably at least 130°C, and up to 160°C, preferably up to 155°C, preferably up to 150°C, preferably up to 145°C, more preferably up to 140°C, even more preferably up to 138°C, still more preferably up to 135°C. In a preferred embodiment, the terpene resin has a softening point of at least 20°C, preferably at least 22°C, more preferably at least 24°C, and up to 50°C, preferably up to 45°C, preferably up to 40°C, more preferably up to 35°C, even more preferably up to 30°C, and even more preferably up to 28°C.

[0069] Bromine number is the amount of bromine (Br2) in grams absorbed by 100 g of sample and is an indicator of the unsaturation of the sample. In some embodiments, the terpene resin used in the inkjet ink has a Bromine Number of at least 12, preferably at least 15, preferably at least 19, preferably at least 22, more preferably at least 25, even more preferably at least 26, still more preferably at least 27, and up to 35, preferably up to 34, preferably up to 33, more preferably up to 32, even more preferably up to 31, and still more preferably up to 30, although terpene resins (e.g., hydrogenated terpene resins) having Bromine Numbers above or below these values ​​may also be used in the disclosed inkjet inks.

[0070] The inkjet inks of the present disclosure can be formulated with a single type of terpene resin or a combination of two or more types of terpene resins. Examples of terpene resins that can be used alone or in combination in the inkjet inks of the present disclosure include PICCOLYTE A115 (Ring and Ball SP=112-118°C, Bromine Number=31.5), PICCOLYTE A125 (Ring and Ball SP=122-128°C, Bromine Number=31.5), PICCOLYTE A135 (Ring and Ball SP=132-138°C, Bromine Number=27), PICCOLYTE A135 PLUS (Ring and Ball SP=132-138°C), PICCOLYTE AO PLUS (oligomer, liquid), PICCOLYTE Examples of suitable resins include, but are not limited to, PINOVA Resin A25 (ring and ball SP = 22-28°C) and PINOVA Resin 2495 (ring and ball SP = 132-138°C, Bromine Number = 27), each of which is formed from high-purity alpha-pinene and is available from Pinova, Inc., and PICCOLYTE S25 (formed from high-purity beta-pinene, ring and ball SP = 22-28°C, Bromine Number = 19), also available from Pinova, Inc.

[0071] In addition to the terpene phenolic resin (A), the inkjet ink may optionally contain other binder resins / tackifiers / adhesives. Such other binder resins / tackifiers / adhesives may be present in an amount of at least 0.1 wt.%, preferably at least 0.5 wt.%, preferably at least 1 wt.%, more preferably at least 1.5 wt.%, even more preferably at least 2 wt.%, even more preferably at least 2.5 wt.%, and up to 10 wt.%, preferably up to 9 wt.%, preferably up to 8 wt.%, preferably up to 7 wt.%, preferably up to 6 wt.%, more preferably up to 5 wt.%, even more preferably up to 4 wt.%, and even more preferably up to 3 wt.%, based on the total weight of the inkjet. Such additional resins, binders, tackifiers or adhesives may include, but are not limited to: Rosin resins, such as those derived from gum rosin, wood rosin, and tall oil rosin (whose main components are resin acids such as abietic acid, palustric acid, neoabietic acid, pimaric acid, isopimaric acid, and / or dehydroabietic acid), including rosin resins formed by modifying the aforementioned rosins, for example, by esterification, hydrogenation (including partial hydrogenation), dimerization, and / or other modification / functionalization (e.g., by Diels-Alder reaction with unsaturated diacids such as maleic or fumaric acid / anhydride, carboxylic acid reduction to the respective aldehydes / alcohols, double bond isomerization, dehydrogenation, oxidation, disproportionation, etc.). Exemplary rosin resins include: (1) Rosin ester resins, such as esters of rosin composed primarily of abietic or pimaric resin acids reacted with alcohol(s), such as glycerin, pentaerythritol, ethylene glycol, diethylene glycol, triethylene glycol, methanol, and the like, optionally hydrogenated or partially hydrogenated, specifically including HARIESTER products available from Harima Chemicals, Inc., STAYBELITE ESTER 10-E and PERMALYN 6110, respectively, available from Eastman, SUPER ESTER A-125, SUPER ESTER A-75, PENSEL D-125, PINECRYSTAL KE-359, available from Arakawa Chemical Industries, Ltd., and FORAL 85, FORAL 105, HERCOLYN products, PEXALYN products, and PENTALYN products available from Pinova; (2) hydrogenated acid rosin such as FORAL AX and FORAL DX, each available from Pinova; (3) partially hydrogenated acidic rosins such as STAYBELITE RESIN-E available from Eastman Co., and STAYBELITE and STAYBELITE A, respectively, available from Pinova Co.; (4) Dimerized rosin, such as POLY-PALE partially dimerized rosin available from Eastman; and (5) functionalized rosin resins, such as esters of rosin (e.g., glycerol esters) modified with maleic anhydride, or rosin subjected to carboxylic acid reducing conditions, specifically, but not limited to, LEWISOL 28-M and Abitol-E hydroabietyl alcohol, each available from Eastman Co.; - phenolic resins (i.e. copolymers of phenolic compounds and formaldehyde), for example novolac resins such as PHENOLITE TD-2131 and PHENOLITE TD-2090 available from DIC Corp.; polyamide resins, such as VERSAMID 725, 744, 756, 759 available from BASF Japan Ltd., TOHMIDE 90, 92, 394-N available from Sanho Chemical Co. Ltd., and SUNMIDE 550, 554, 615A, 638, 640 available from Evonik; - epoxy resins, including sulfonamide-modified epoxy resins, such as AD-PRO MTS available from Rit-Chem; (Meth)acrylate and styrene / (meth)acrylate resins, such as JONCRYL 63, JONCRYL 67, JONCRYL 586, JONCRYL 611, JONCRYL 682, JONCRYL 693 available from BASF, PARALOID DM-55 and PARALOID B-66 available from Palmer Holland, PARALOID B-72 available from Dow Chemical (USA), and ELVACITE 2013 available from Lucite Inc.; polyurethane resins, such as those formed from the reaction of (i) polyols, including but not limited to ethylene glycol, propylene glycol, propanediol, butanediol, polyethylene glycol, polypropylene glycol, polytetrahydrofuran diol, 3-methyl-1,5-pentanediol, 1,9-nonanediol, polyester polyols such as polyethylene glycol adipate diol, polyethylene glycol succinate diol, poly(3-methyl-1,5-pentanediol adipate) glycol, poly(3-methyl-1,5-pentanediol terephthalate) glycol, and carbonate polyols, with (ii) diisocyanates, including but not limited to 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4-diphenylmethane diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate, e.g., PERMAX 200, PERMAX available from Lubrizol; 202, and SANCURE 20025F; - polyvinyl butyral resins, such as PIOLOFORM BN16 and MOWITAL B20H available from Kuraray America, Inc.; - polyhydroxystyrene resins, such as poly(p-hydroxystyrene) from DuPont; vinyl resins, such as UCAR VYHH, VMCH, VMCA, and VAGF available from The Dow Chemical Company, and VINNOL E15 / 45, H14 / 36, E15 / 45M, and E16 / 40A available from Wacker Chemie AG (Germany); - Formaldehyde resins, including sulfonamide-modified formaldehyde resins such as p-toluenesulfonamide formaldehyde resins, melamine formaldehyde resins, and sulfonamide-modified melamine formaldehyde resins; - cellulose ester resins such as cellulose acetate butyrate (CAB-551-0.01) available from Eastman; - as well as polyesters, sulfonated polyesters, gums, cellulose ethers, cellulose nitrate resins, polymaleic anhydride, acetal polymers, styrene / butadiene copolymers, ketone-aldehyde resins, and polyketone resins; - and equivalents, including mixtures thereof.

[0072] In some embodiments, the inkjet ink is substantially free of terpene resins. In some embodiments, other than the terpene phenolic resin (A) and any optional terpene resins, the inkjet ink is substantially free of additional binder resins / tackifiers / adhesives, as described above. In some embodiments, the terpene phenolic resin (A) is the only resin present in the disclosed inkjet inks. In some embodiments, the inkjet ink is substantially free of rosin resins. In some embodiments, the inkjet ink is substantially free of rosin ester resins, partially hydrogenated acidic rosins, dimerized rosins, and other functionalized / modified rosin resins. In some embodiments, the inkjet ink is substantially free of phenolic resins. In some embodiments, the inkjet ink is substantially free of polyamide resins. In a preferred embodiment, the terpene phenolic resin (A) is the only tackifier or adhesive resin present in the inkjet ink.

[0073] The terpene phenolic resin (A) has been found to provide excellent decap time and adhesion when used in combination with a solvent system (B) containing ethanol (B1) and a co-solvent (B2) and an amine-modified silicone. Without being bound by theory, it is believed that the terpene phenolic resin (A) improves the decap behavior of inkjet inks by forming a thin "skin" or coating within the printhead nozzles, thereby forming a temporary seal to prevent or reduce solvent loss during periods of inactivity, but the "skin" can be easily destroyed once printing resumes. It is believed that the polarity of the terpene phenolic resin (A) is high enough to dissolve the vehicle, but not so high that it interacts too strongly with the solvent system to prevent "skin" formation.

[0074] <(B) Solvent system> In many printing processes utilizing solvent-based inks, particularly thermal inkjet printing, the selection of an appropriate solvent system can affect the reliability of the printing process, the properties / appearance of the printed ink product, and the efficiency of the overall printing process. For example, in thermal inkjet printing, the selection of a solvent system can: 1) aid in bubble formation during the jetting process, resulting in reliable ink jetting; 2) affect the stability / volatility of the inkjet ink by changing the interaction dynamics between the solvent(s) and various inkjet ink components, thus affecting decap behavior, kogation, running stability, and / or drop trajectory; 3) affect the adhesion, rub resistance, scratch resistance, and optical density properties of the printed image through interaction forces between the solvent system and other inkjet ink components, even if the solvent is no longer present after drying or is present in small amounts; 4) affect the drying time after application or the equipment required to dry the applied ink; and / or 5) may affect droplet dynamics.

[0075] In view of the above, particular preference is given herein to inkjet inks having a solvent system (B) comprising (B1) ethanol and (B2) a cosolvent. Examples of suitable cosolvents include, but are not limited to: alcohols other than ethanol, such as 1-propanol, 2-propanol, 1-butanol, 2-butanol, tert-amyl alcohol, 2-methyl-1-butanol, undecanols (e.g. 1-undecanol), dodecanols (e.g. 1-dodecanol), tridecanols (e.g. 1-tridecanol), tetradecanols (e.g. 1-tetradecanol), terpene alcohols, such as monoterpene alcohols (e.g. terpineol, geraniol, citronellol, linalool, etc.); ketones, such as acetone, methyl ethyl ketone, diethyl ketone, diphenyl ketone, dibenzyl ketone, acetophenone, cyclopentanone, methyl isopropyl ketone, methyl n-propyl ketone, ethyl isopropyl ketone (also known as 2-methyl-3-pentanone), 2-hexanone (also known as methyl butyl ketone), methyl isobutyl ketone, 3-hexanone, 3-pentanone, 2-pentanone, cyclohexanone, and diacetone alcohol; ethers, such as dimethyl ether, diethyl ether, dipropyl ether, methyl tert-butyl ether, tetrahydrofuran, 1,4-dioxane, dibutyl ether, and di-tert-butyl ether; - glycol ethers, including monoalkyl glycol ethers, dialkyl glycol ethers, and monoalkyl monoester glycol ethers, such as ethylene glycol monomethyl ether (2-methoxyethanol), ethylene glycol monoethyl ether (2-ethoxyethanol), ethylene glycol mono-isopropyl ether (2-isopropoxyethanol), ethylene glycol mono-n-propyl ether (2-propoxyethanol), ethylene glycol mono-t-butyl ether, ethylene glycol monobutyl ether, ethylene glycol mono-isobutyl ether, ethylene glycol monophenyl ether (2-phenoxyethanol), ethylene glycol monobenzyl ether (2-benzyloxyethanol), diethylene glycol monomethyl ether (2-(2-methoxyethoxy)ethanol), diethylene glycol monomethyl ether (2-(2-methoxyethoxy)ethanol), Glycol monoethyl ether (2-(2-ethoxyethoxy)ethanol), propylene glycol monomethyl ether (1-methoxy-2-propanol), propylene glycol monoethyl ether, propylene glycol mono-t-butyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-isopropyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, propylene glycol methyl ether acetate, ethylene glycol dimethyl ether (dimethoxyethane), ethylene glycol diethyl ether (diethoxyethane), diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol mono-n-propyl ether; esters, such as methyl acetate, ethyl acetate, n-butyl acetate, methyl lactate, ethyl lactate, butyl lactate, methoxyethyl acetate, ethoxyethyl acetate, methoxypropyl acetate, and ethoxypropyl acetate; - acetals such as 1,3-dioxolane; - Amides such as dimethylformamide and dimethylacetamide - acetonitrile; - and mixtures of two or more of them.

[0076] In some embodiments, the co-solvent (B2) preferably has a viscosity of 16.5 (cal / cm 3 ) 1 / 2 Less than 16 (cal / cm 3 ) 1 / 2 Less than 15 (cal / cm 3 ) 1 / 2 Less than 14 (cal / cm 3 ) 1 / 2 Less than 13.5 (cal / cm 3 ) 1 / 2 less than 13.0 (cal / cm 3 ) 1 / 2 Less than 12.5 (cal / cm 3 ) 1 / 2 Less than 12 (cal / cm 3 ) 1 / 2 has a solubility parameter that is less than

[0077] In some embodiments, a preferred co-solvent (B2) is n-propanol (solubility parameter 12.0 (cal / cm 3 ) 1 / 2 ), methyl ethyl ketone (solubility parameter 9.0 (cal / cm 3 ) 1 / 2 ), ethyl acetate (solubility parameter 9.1 (cal / cm 3 ) 1 / 2 ), propylene glycol monomethyl ether (solubility parameter 11.2 (cal / cm 3 ) 1 / 2 ) and 1,3-dioxolane (solubility parameter 8.6 (cal / cm 3 ) 1 / 2 ) is at least one selected from the group consisting of

[0078] In some embodiments, the solvent system is substantially free of 1-methoxy-2-propanol, hi some embodiments, the solvent system is substantially free of butyl propionate.

[0079] The amount of ethanol (B1) preferred to achieve desired ink properties (e.g. decap behavior, adhesion, etc.) is at least 50% by weight, preferably at least 55% by weight, preferably at least 60% by weight, preferably at least 65% by weight, preferably at least 70% by weight, preferably at least 75% by weight, preferably at least 80% by weight, and may range up to 98% by weight, preferably up to 97% by weight, preferably up to 96% by weight, more preferably up to 94% by weight, even more preferably up to 92% by weight, still even more preferably up to 90% by weight, even even more preferably up to 88% by weight, based on the total weight of said inkjet.

[0080] The co-solvent (B2) may be present in the inkjet ink in an amount of at least 0.5 wt.%, preferably at least 1 wt.%, preferably at least 2 wt.%, preferably at least 3 wt.%, preferably at least 4 wt.%, preferably at least 5 wt.%, more preferably at least 6 wt.%, more preferably at least 7 wt.%, more preferably at least 8 wt.%, and up to 45 wt.%, preferably up to 40 wt.%, preferably up to 35 wt.%, preferably up to 30 wt.%, preferably up to 25 wt.%, more preferably up to 20 wt.%, even more preferably up to 18 wt.%, even more preferably up to 16 wt.%, and still more preferably up to 15 wt.%, based on the total weight of the inkjet.

[0081] In a preferred embodiment, the ethanol (B1) together with the co-solvent (B2) constitutes the majority of the solvent system (B) used in the inkjet ink, i.e. the combined weight of the ethanol (B1) and the co-solvent (B2) may be in the range of at least 50 wt.-%, preferably at least 60 wt.-%, more preferably at least 70 wt.-%, preferably at least 80 wt.-%, preferably at least 90 wt.-%, preferably at least 95 wt.-%, preferably at least 96 wt.-%, based on the total weight of the solvent system (B).

[0082] Relative to ethanol (B1), preferred inkjet inks are those having a weight ratio of ethanol (B1) to said co-solvent (B2) ((B1):(B2)) in the range of from 1:1, more preferably from 1.25:1, more preferably from 1.5:1, more preferably from 1.75:1, more preferably from 2:1, more preferably from 3:1, more preferably from 4:1, and preferably up to 25:1, more preferably up to 22.5:1, more preferably up to 20:1, more preferably up to 17.5:1, more preferably up to 15:1, more preferably up to 12.5:1, more preferably up to 11:1, more preferably up to 9:1.

[0083] Relative to the terpene phenolic resin (A), preferred inkjet inks are those having a weight ratio of ethanol (B1) to said terpene phenolic resin (A) ((B1):(A)) in the range of at least 20:1, preferably at least 25:1, preferably at least 30:1, preferably at least 35:1, preferably at least 40:1, preferably at least 45:1, preferably at least 50:1, preferably at least 55:1, preferably at least 60:1, and up to 250:1, preferably up to 225:1, preferably up to 200:1, preferably up to 175:1, preferably up to 150:1, more preferably up to 125:1, more preferably up to 120:1, more preferably up to 115:1, more preferably up to 110:1, even more preferably up to 105:1, still even more preferably up to 100:1, still even more preferably up to 95:1, and even even more preferably up to 90:1.

[0084] The amount of co-solvent (B2) can be adjusted, for example, to provide the desired level of solvation, but preferred inkjet inks are those having a weight ratio of terpene phenolic resin (A) to co-solvent (B2) ((A):(B2)) of at least 1:75, preferably at least 1:70, preferably at least 1:65, preferably at least 1:60, preferably at least 1:55, preferably at least 1:50, preferably at least 1:45, preferably at least 1:42.5, more preferably at least 1:40, more preferably at least 1:37.5, more preferably at least 1:35, even more preferably at least 1:32.5, still even more preferably at least 1:30, and up to 1:2, preferably up to 1:5, preferably up to 1:7, preferably up to 1:7.5, more preferably up to 1:8.

[0085] The other organic solvent(s), excluding ethanol (B1) and the co-solvent (B2), can be used in any amount desired for a particular application, with typical loadings ranging from up to 20 wt %, preferably up to 15 wt %, preferably up to 10 wt %, preferably up to 5 wt %, more preferably up to 4 wt %, even more preferably up to 2 wt %, and even more preferably up to 1 wt %, based on the total weight of the inkjet ink, although higher loadings may also be used. In some embodiments, the inkjet ink is substantially free of methanol. In some embodiments, the inkjet ink is substantially free of polyols (also known as glycols), such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, neopentyldiol, 1,6-hexanediol, and 2-methyl-2,4-pentanediol. In some embodiments, the inkjet ink is substantially free of other organic solvents.

[0086] In some embodiments, the inkjet ink is substantially free of solvents having a boiling point greater than 255°C, preferably greater than 250°C, preferably greater than 245°C, preferably greater than 240°C, preferably greater than 235°C, preferably greater than 230°C, preferably greater than 220°C, preferably greater than 210°C, more preferably greater than 200°C, and even more preferably greater than 195°C.

[0087] In a preferred embodiment, the solvent system (B) consists of ethanol (B1) and a co-solvent (B2).

[0088] In a preferred embodiment, the inkjet ink of the present disclosure is substantially non-aqueous, meaning that no water is added to the inkjet ink other than what may be incidental amounts of moisture from ambient conditions. In such cases, the inkjet ink may have less than 1 wt. % water, preferably less than 0.5 wt. %, preferably less than 0.1 wt. %, more preferably less than 0.05 wt. %, even more preferably less than 0.01 wt. %, and even more preferably 0 wt. % water, based on the total weight of the inkjet ink.

[0089] <Amine-modified silicone (C)> The amine-modified silicone may be a block copolymer having a pendant graft structure comprising (i) a silicone backbone (main chain), (ii) one or more organic amine side chains attached to the silicone backbone, and optionally (iii) one or more fatty alkyl side chains attached to the silicone backbone, or the pendant graft structure may comprise (i), (ii), and optionally (iii). Thus, as long as at least one organic amine side chain is attached to the silicone backbone, the material meets the definition of "amino-modified silicone," regardless of whether additional side chain types (e.g., fatty alkyl side chains) are also attached to the silicone backbone. Preferably, no side chains other than the organic amine side chains and, optionally, the fatty alkyl side chains are present in the amine-modified silicone.

[0090] As referred to herein, the "side chains" are attached to the silicone backbone (main chain) as pendant grafts, rather than as a continuation of the silicone backbone, as is the case with linear block copolymers such as ABA structures, thereby forming branch points on the silicone backbone from which the side chains extend via covalent bonds. Preferred organoamine-modified silicones are non-hydrolyzable, i.e., the side chains are attached to the silicone backbone via Si-C bonds.

[0091] <(i) Silicone Backbone> The silicone backbone can be formed by polymerization and / or polycondensation of suitably functionalized silanes, and can be based on any organosilicon polymer or oligomer (polyorganosiloxane) of variable molecular weight, linear or branched structure, having a polysiloxane backbone structure (silicon atoms bonded via oxygen atoms, -Si-O-Si-) with alkyl groups, aryl groups, and / or arylalkyl groups directly bonded to (tetravalent) silicon atoms. For example, the polyorganosiloxane backbone may be a linear structure, including, but not limited to, a polydimethylsiloxane (dimethicone) backbone (wherein each silicon atom in the backbone is directly bonded to two methyl groups), a poly(dimethylsiloxane-co-methylphenylsiloxane) backbone, a poly(dimethylsiloxane-co-diphenylsiloxane) backbone, and a poly(dimethylsiloxane-co-methylalkylsiloxane) backbone; or a branched structure, of which particular mention is made of polydimethylsiloxyethyl dimethicone.

[0092] <(ii) Organic Amine Side Chain> The amine-modified silicone comprises at least one organic amine side chain, which is based on an organic amine or an amine-containing polymer (e.g., polyaziridine), for example, formed by ring-opening polymerization of one or more alkyleneimines (ethyleneimine (aziridine) and propyleneimine are most preferred), including copolymers, for example, block copolymers thereof. Preferably, the organic amine side chain is an alkylamine, arylamine, arylalkylamine, fatty amine, or polyaziridine extending from the silicone backbone.

[0093] The organic amine side chains may include primary amines, secondary amines, tertiary amines, or combinations thereof. Such amines may be present in any suitable number, e.g., from 1 to 1,000. In some embodiments, preferred organic amine side chains are selected from the group consisting of monoamines comprising primary amines and diamines comprising primary and secondary amines. Such monoamines may be alkylamines, arylamines, arylalkylamines, or fatty amines. Such diamines may be alkylamines, arylamines, arylalkylamines, or fatty amines.

[0094] (iii) Fatty Alkyl Side Chains The amine-modified silicone may also be optionally modified with one or more fatty alkyl side chains, for example, those containing at least 8 carbon atoms, preferably at least 10 carbon atoms, more preferably at least 12 carbon atoms, and up to 22 carbon atoms, preferably up to 20 carbon atoms, more preferably up to 18 carbon atoms, even more preferably up to 16 carbon atoms, and even more preferably up to 14 carbon atoms. Examples of fatty alkyl side chain groups include, but are not limited to, capryl, nonyl, decyl, undecyl, lauryl, tridecyl, myristyl, pentadecyl, cetyl, palmitoleyl, heptadecyl, stearyl, oleyl, arachidyl, and behenyl, and specific examples include lauryl, myristyl, cetyl, and stearyl, preferably lauryl.

[0095] <(iv) Polyether Side Chain> The amine-modified silicone may optionally be modified with one or more polyether side chains. The polyether side chains may be based on polyalkylene glycol oligomers or polymers, such as those formed by ring-opening polymerization of one or more alkylene oxides, with ethylene oxide (EO), propylene oxide (PO), and / or butylene oxide (BO) being most preferred, including copolymers thereof, such as block copolymers. Preferably, the polyether side chains are polyethylene glycol or polyethylene glycol-polypropylene glycol copolymers extending from the silicone backbone, and more preferably, the polyether side chains are polyethylene glycol side chains formed solely from ethylene oxide, EO.

[0096] Polyether side chains of various lengths can be utilized. Typically, the number of moles of alkylene oxide units per side chain ranges from at least 2, preferably at least 3, more preferably at least 4, even more preferably at least 5, still more preferably at least 6, and up to 50, preferably up to 40, preferably up to 30, preferably up to 20, preferably up to 15, more preferably up to 12, even more preferably up to 10, and still more preferably up to 9, with 3 to 10 moles, preferably 4 to 9 moles, of ethylene oxide (EO) units per side chain being particularly preferred.

[0097] Additionally, any polyether side chains present may be uncapped (whereby the end of the polyether side chain opposite the silicone backbone terminates with -H, forming a terminal hydroxyl functionality), or capped with alkyl groups having 1, 2, 3, or 4 carbon atoms (including methyl, ethyl, propyl, and butyl, among others), forming a terminal alkyl ether group.

[0098] In some embodiments, the amine-modified silicone is a block copolymer having pendant graft structures, such as represented by formula (IA):

[0099] [ka]

[0100] During the ceremony, o is 0 or a positive integer, for example at least 1, preferably at least 2, more preferably at least 3, even more preferably at least 4, even more preferably at least 5, and up to 500, preferably up to 400, preferably up to 300, more preferably up to 200, even more preferably up to 100, even more preferably up to 50; p represents the number of constitutional units comprising said organic amine side chains and is a positive integer, for example at least 1, preferably at least 2, more preferably at least 3, even more preferably at least 4, even more preferably at least 5, and up to 100, preferably up to 80, preferably up to 60, more preferably up to 40, even more preferably up to 20, even more preferably up to 10; A is an amine-containing group (organoamine) as described above.

[0101] The amine-modified silicone with pendant graft structures is formed from a linear polydimethylsiloxane backbone containing one or more organic amine side chains.

[0102] In some embodiments, the amine-modified silicone is a block copolymer having a pendant graft structure, optionally with one or more fatty alkyl or polyether side chains as described above. In some embodiments, the amine-modified silicone is a block copolymer having a pendant graft structure, the pendant graft structure having a branched polydimethylsiloxane backbone containing one or more organic amine side chains and, optionally, one or more fatty alkyl or polyether side chains as described above.

[0103] In some embodiments, the inkjet ink is substantially free of silicones lacking amine functionality. Examples of such silicones include unmodified silicones (e.g., those without side chains containing non-siloxane functional groups) and modified silicones containing only non-amine functional groups, such as polyether-modified silicones (e.g., those with only polyether side chains), mercapto-modified silicones, vinyl-modified silicones, silanol-modified silicones, hydride-modified silicones, epoxy-modified silicones, (meth)acrylate-modified silicones, carboxylate-modified silicones, and haloalkyl-modified silicones. In some embodiments, the inkjet ink is free of silicones lacking amine functionality. That is, the inkjet ink is free of silicones lacking amine functionality. In such embodiments, the amine-modified silicone is the only silicone present in the inkjet ink. In some embodiments in which the inkjet ink is free of silicones lacking amine functionality, the amine-modified silicone can comprise or consist of other functional groups, such as those listed above. In some embodiments where the inkjet ink lacks silicones lacking amine functionalization, the amine-modified silicones do not comprise or consist of other functional groups, i.e., the inkjet ink does not comprise silicones that do not have amine functionalization, and the amine-modified silicone(s) present do not comprise non-amine functional groups.

[0104] In some embodiments, the viscosity of the amine-modified silicone (C) measured at 25°C is 2 / s, preferably at least 25, preferably at least 30, preferably at least 35, preferably at least 40, preferably at least 45, preferably at least 50, preferably at least 55, preferably at least 60, and up to 250, preferably up to 240, preferably up to 230, preferably up to 220, preferably up to 210, preferably up to 200, preferably up to 190, preferably up to 180, preferably up to 170, preferably up to 160, preferably up to 150, preferably up to 140, preferably up to 130, preferably up to 120, preferably up to 110 mm 2 / s.

[0105] In some embodiments, the amine-modified silicone preferably has an amine functional group equivalent weight (FGEW) of 350 to 11,000 g / mol, preferably 1,000 to 9,000 g / mol, preferably 1,500 to 8,800 g / mol, preferably 1,700 to 7,600 g / mol, preferably 2,000 to 7,000 g / mol, preferably 3,000 to 6,500 g / mol, preferably 5,000 to 6,000 g / mol. The functional group equivalent weight refers to the weight of the amine-modified silicone containing one formula amount of amine functional groups.

[0106] Suitable examples of the amine-modified silicone that can be employed in the disclosed inkjet ink include KF-865 (monoamino, functional group equivalent weight (FGEW) = 5,000), KF-868 (monoamino, FGEW = 8,800), KF-864 (monoamino, FGEW = 3,800), KF-859 (diamino, FGEW = 6,000), KF-393 (diamino, FGEW = 350), KF-860 (diamino, FGEW = 7,600), and KF-880 (diamino). Examples of suitable amine-modified silicones include, but are not limited to, KF-8004 (diamino, FGEW=1,500), KF-8002 (diamino, FGEW=1,700), KF-8005 (diamino, FGEW=11,000), KF-867 (diamino, FGEW=1,700), KF-8021 (diamino, FGEW=55,000), KF-869 (diamino, FGEW=3,800), and KF-861 (diamino, FGEW=2,000). Each is available from Shin-Etsu Chemical Co., Ltd. Particularly preferred amine-modified silicones are KF-859 and KF-865.

[0107] The amine modified silicone (C) may be present in the inkjet in an amount of at least 0.1 wt.%, preferably at least 0.125 wt.%, preferably at least 0.150 wt.%, preferably at least 0.175 wt.%, preferably at least 0.19 wt.%, preferably at least 0.20 wt.%, and up to 10 wt.%, preferably up to 7.5 wt.%, preferably up to 5 wt.%, preferably up to 2.5 wt.%, preferably up to 2.0 wt.%, preferably up to 1.5 wt.%, preferably up to 1.25 wt.%, preferably up to 1.2 wt.%, based on the total weight of the inkjet.

[0108] <Alkanolamine (D)> Alkanolamines are alkane-based compounds that contain both a hydroxyl (-OH) group and an amino (primary, secondary, or tertiary) group.

[0109] In some embodiments, the alkanolamine (D) has a total of at least 2 carbon atoms, preferably at least 3 carbon atoms, preferably at least 4 carbon atoms, and up to 8 carbon atoms, preferably up to 7 carbon atoms, more preferably up to 6 carbon atoms, more preferably up to 5 carbon atoms.

[0110] In a preferred embodiment, the alkanolamine (D) used in the inkjet ink herein has the following general formula II:

[0111] [ka]

[0112] During the ceremony, X, Y and Z are independently -hydrogen; -C1 to C5 alkyl group, preferably C2 to C3 alkyl group; and - an alkanol group, preferably a C2 to C5 alkanol group, more preferably a C3 to C4 alkanol group selected from the group consisting of: At least one of X, Y and Z is an alkanol group (an alkyl substituent having at least one hydroxyl group).

[0113] In some embodiments, one of X, Y, and Z is an alkanol group. In some embodiments, two of X, Y, and Z are alkanol groups. In some embodiments, all of X, Y, and Z are alkanol groups.

[0114] With respect to one or more alkanol groups, the alkyl chain may contain branching. Alternatively, the alkyl chain of the alkanol group may be linear (without alkyl branching). In a preferred embodiment, the alkanol group is based on a linear alkyl chain. Furthermore, the carbon bearing the hydroxyl group of the alkanol group may be a primary, secondary, or tertiary carbon, and preferably the carbon bearing the hydroxyl group is a primary or secondary carbon.

[0115] The alkanolamine (D) may contain primary amino groups (i.e., two of X, Y, and Z are hydrogen), secondary amino groups (i.e., one of X, Y, and Z is hydrogen), or tertiary amino groups (i.e., all of X, Y, and Z are non-hydrogen). When an alkanolamine (D) containing secondary amino groups is used, the two non-hydrogen substituents may be the same or different alkanol groups, preferably the same alkanol group, as in, for example, diethanolamine. When an alkanolamine (D) containing tertiary amino groups is used, the three non-hydrogen substituents may be the same or different alkanol groups, preferably the same alkanol group, as in, for example, triethanolamine.

[0116] Suitable examples of the alkanolamine (D) include, but are not limited to, ethanolamine, N-methylethanolamine, N,N-dimethylethanolamine, N-ethylethanolamine, N-propylethanolamine, N-isopropylethanolamine, N,N-diisopropylethanolamine, N-butylethanolamine, diethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, triethanolamine, propanolamine (3-amino-1-propanol), N-methylpropanolamine, N,N-dimethylpropanolamine, dipropanolamine, tripropanolamine, isopropanolamine, N,N-dimethylisopropanolamine, diisopropanolamine, triisopropanolamine, 2-amino-2-methyl-1-propanol, 2-amino-2-ethyl-1,3-propanediol, 4-amino-1-butanol, 2-amino-1-butanol, sec-butanolamine, and di-sec-butanolamine. In a preferred embodiment, the alkanolamine (D) is at least one selected from the group consisting of ethanolamine, propanolamine (3-amino-1-propanol), isopropanolamine, diethanolamine, and triethanolamine.

[0117] In some embodiments, the alkanolamine (D) is present in the inkjet ink in an amount of at least 0.01 wt%, more preferably 0.1 wt%, even more preferably 0.2 wt%, and preferably up to 5 wt%, preferably up to 4 wt%, preferably up to 3 wt%, preferably up to 2.5 wt%, preferably up to 2 wt%, preferably up to 1.5 wt%, preferably up to 1 wt%, based on the total weight of the inkjet ink. In some embodiments, the weight ratio of the terpene phenolic resin (A) to the alkanolamine (D) ((A):(D)) is at least 0.25:1, preferably at least 0.5:1, preferably at least 0.6:1, preferably at least 1:1, and up to 2.5:1, preferably up to 2:1, preferably up to 1.75:1, preferably up to 1.5:1, preferably up to 1.25:1.

[0118] <Colorant (E)> Those skilled in the art will readily appreciate that the inkjet ink may optionally contain one or more colorants (E) to provide a colored ink. In other words, the inkjet of the present invention may further contain a colorant (E), which may be used for various printing purposes, and the inkjet ink is not limited to a specific color. Any colorant (E) may be used in the inkjet ink to provide a desired color, including dyes, pigments, mixtures thereof, etc., provided that the colorant (E) can be dissolved or dispersed in the inkjet ink. Suitable colors include, for example, cyan, magenta, yellow, and key (black) (“CMYK”), white, orange, green, light cyan, light magenta, violet, etc., including both spot colors and process colors.

[0119] The inkjet ink can contain various dyes. The inkjet ink can contain various inorganic and / or organic pigments. These pigments not only impart color to the inkjet ink, but also improve the lightfastness and weather resistance of the printed image.

[0120] Preferably, the inkjet ink of the present disclosure comprises a colorant (E) comprising a metal complex azo dye. In this context, the term "metal complex azo dye" refers to a dye comprising a compound formed from a metal center and a ligand containing an azo functionality (also known as a diazenyl functionality). Typically, the ligand containing an azo functionality is a molecule that is itself considered an azo dye.

[0121] The ligand containing the azo functionality coordinates to a metal center, typically a transition metal or main group metal or metalloid, but not to an alkali metal or alkaline earth metal. Examples of suitable metals that can form the metal center include, but are not limited to, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, zirconium, niobium, molybdenum, ruthenium, rhodium, cadmium, aluminum, indium, tin, bismuth, and mixtures thereof. Such coordination can occur via any suitable functional group present on the ligand. Examples of such functional groups include, but are not limited to, oxygen-containing functional groups such as alcohols, alkoxides, carboxylic acids and carboxylate salts, esters, ketones, and ethers; nitrogen-containing functional groups such as amines, amides, azides, diazenyls (azo groups), imines, porphyrins, imides, isonitriles, nitriles, and nitro functional groups; phosphorus-containing functional groups such as phosphines, phosphites, phosphates, phosphonites, phosphonates, phosphinites, and phosphinate functional groups; and sulfur-containing functional groups such as thiols, thiolates, disulfides, sulfones, sulfonic acids and sulfonates, sulfoxides, thials, thioesters, thiosulfinates, thiocarboxylic acids and thiocarboxylate salts, sulfinic acids and sulfonates, thiocyanates, and isothiocyanate functional groups. The ligands coordinating to the metal center may be monodentate, bidentate, tridentate, or tetradentate. Typically, the azo-containing ligands used herein form a coordination interaction with the metal center through one or both of the nitrogen atoms forming the azo group.

[0122] In general, the remainder of the inner coordination sphere of the metal center can be further filled with any suitable ligand or combination of ligands known to those skilled in the art. Examples of suitable ligands include species having oxygen-containing functional groups such as alcohols, alkoxides, hydroxides, carboxylic acids and carboxylate salts, esters and ethers; species having nitrogen-containing functional groups such as amines (herein understood to include ammonia), amides, azides, other diimides (also known as azo compounds), imines, porphyrins, imides, isonitriles, nitriles, nitro compounds; species having phosphorus-containing functional groups such as phosphines, phosphites, phosphates, phosphonites, phosphonates, phosphinites, phosphinates; species having sulfur-containing functional groups such as thiols, thiolates, disulfides, sulfones, sulfonic acids and sulfonates, sulfoxides, thials, thioesters, thiosulfinates, thiocarboxylic acids and thiocarboxylate salts, sulfinic acids and sulfinates, thiocyanates and isothiocyanates; hydrocarbons containing one or more π-electron systems such as mesitylene, cyclopentadienyl anion, cyclooctadecene; halides; and water. In general, the ligands can be monodentate, bidentate, tridentate, tetradentate, or pentadentate, as appropriate. However, hexadentate ligands, such as ethylenediaminetetraacetic acid (EDTA), are not suitable because they do not leave an open coordination site for a suitable ligand containing an azo functionality. In general, the functional group can occupy any suitable position on the molecule that serves as the ligand. For example, the alcohol or amine can be a primary alcohol or amine, a secondary alcohol or amine, or a tertiary alcohol or amine, as appropriate.

[0123] In a preferred embodiment, the metal complex azo dye is a metal complex comprising a metal center and (E)-1-((2-methoxy-5-nitrophenyl)diazenyl)naphthalen-2-ol or its deprotonated, demethylated, deprotonated and demethylated forms, tautomers or stereoisomers. The structure of (E)-1-((2-methoxy-5-nitrophenyl)diazenyl)naphthalen-2-ol is shown in Formula III below:

[0124] [ka]

[0125] To form a suitable metal complex, (E)-1-((2-methoxy-5-nitrophenyl)diazenyl)naphthalen-2-ol can exist in a deprotonated form in which the hydroxyl group is deprotonated to form an alkoxide-type ligand (see formula (IV-A) below), a demethylated form in which the methoxy group is converted to an alkoxide-type ligand (see formula (IV-B) below), or a deprotonated and demethylated form in which the hydroxyl group is deprotonated to form an alkoxide-type ligand and the methoxy group is converted to an alkoxide-type ligand (see formula (IV-C) below).

[0126] [ka] [ka] [ka]

[0127] In preferred embodiments, the metal center is a chromium ion. In some embodiments, the chromium ion is in the +3 oxidation state. In such embodiments, the metal complex may have a positive charge, a negative charge, or no charge. In embodiments in which the metal complex has a positive charge, the metal complex azo dye may further comprise any suitable anion for charge balance. Examples of such suitable anions include, but are not limited to, carboxylate, halide, sulfate, phosphate, hydrogen phosphate, dihydrogen phosphate, nitrate, and mixtures thereof. In embodiments in which the metal complex has a negative charge, the metal complex azo dye may further comprise any suitable cation for charge balance. Examples of such suitable cations include, but are not limited to, alkali metals, alkaline earth metals, ammonium compounds, and mixtures thereof.

[0128] Examples of suitable metal complex azo dyes include, but are not limited to, Solvent Black 27, Solvent Black 28, Solvent Black 29, Solvent Black 34, Solvent Blue 137, Solvent Brown 37, Solvent Brown 42, Solvent Brown 43, Solvent Brown 52, Solvent Orange 54, Solvent Red 8, Solvent Red 109, Solvent Red 119, Solvent Red 122, Solvent Yellow 19, Solvent Yellow 21, Solvent Yellow 25, Solvent Yellow 82, Solvent Yellow 88, Solvent Yellow 146, Solvent Violet 58, Solvent Violet 61, and VALIFAST BLACK 3870, VALIFAST RED 1355, and VALIFAST YELLOW 3150, each available from Orient Chemical Industry Co., Ltd. Examples of suitable metal complex azo dyes include Solvent Black 29 (also sold by Orient Chemical Industry Co., Ltd. as VALIFAST BLACK 3870) and Solvent Red 122 (also sold by Orient Chemical Industry Co., Ltd. as VALIFAST RED 3312), among others.

[0129] The colorants may be included in the inkjet ink to provide any desired color, including dyes, pigments, mixtures thereof, etc., provided that the colorants are soluble or stably dispersible within the inkjet ink. Suitable colors include, for example, cyan, magenta, yellow, and key (black) (“CMYK”), white, orange, green, light cyan, light magenta, violet, etc., including both spot colors and process colors.

[0130] In some embodiments, colorant (E) is present in an amount of preferably at least 0.1 wt.%, more preferably at least 0.5 wt.%, more preferably at least 1 wt.%, more preferably at least 2 wt.%, more preferably at least 3 wt.%, and preferably up to 20 wt.%, more preferably up to 15 wt.%, more preferably up to 10 wt.%, more preferably up to 8 wt.%, more preferably up to 7 wt.%, based on the total weight of the inkjet ink.

[0131] Those skilled in the art will readily understand that the inkjet ink can optionally include one or more additional colorants (E2) to provide a colored ink that can be used for various printing purposes, and that the inkjet ink is not limited to a particular color. Any additional colorant (E2), including dyes, pigments, mixtures thereof, and the like, can be used in the inkjet ink to provide a desired color, provided that the additional colorant (E2) can be dissolved or dispersed within the inkjet ink. Suitable colors include, for example, cyan, magenta, yellow, and key (black) (“CMYK”), white, orange, green, light cyan, light magenta, violet, and the like, including both spot colors and process colors. Generally, the additional colorant (E2) may be used in an amount of at least 0.1 wt. %, preferably at least 0.5 wt. %, preferably at least 1 wt. %, preferably at least 2 wt. %, preferably at least 3 wt. %, and up to 20 wt. %, preferably up to 15 wt. %, preferably up to 10 wt. %, preferably up to 8 wt. %, and preferably up to 7 wt. %, based on the total weight of the inkjet ink.

[0132] The inkjet ink may contain various inorganic and / or organic pigments, which not only impart color to the inkjet ink but also improve the lightfastness and weather resistance of the printed image.

[0133] <Surfactant (F)> The inkjet inks of the present disclosure can optionally include (F) surfactants, for example, to provide anti-blocking, ink receptivity, leveling, anti-cratering, increased surface slip, and / or substrate wetting properties, among other benefits, without sacrificing the decap and adhesion performance of the inkjet ink. If used, the amount of surfactant (F) used may be in the range of at least 0.01 wt.-%, preferably at least 0.015 wt.-%, preferably at least 0.02 wt.-%, preferably at least 0.04 wt.-%, more preferably at least 0.06 wt.-%, even more preferably at least 0.08 wt.-%, even more preferably at least 0.1 wt.-%, even more preferably at least 0.15 wt.-%, even more preferably at least 0.2 wt.-%, even more preferably at least 0.25 wt.-%, even more preferably at least 0.3 wt.-%, even more preferably at least 0.35 wt.-%, even more preferably at least 0.4 wt.-%, even more preferably at least 0.45 wt.-%, even more preferably at least 0.5 wt.-%, and up to 5 wt.-%, preferably up to 4 wt.-%, preferably up to 3 wt.-%, preferably up to 2 wt.-%, preferably up to 1 wt.-%, preferably up to 0.95 wt.-%, preferably up to 0.9 wt.-%, even more preferably up to 0.85 wt.-%, even more preferably up to 0.8 wt.-%, based on the total weight of said inkjet.

[0134] Examples of surfactants (F) that may be used herein alone or in combination include, but are not limited to: - polysiloxanes, including organo-modified silicones (e.g., alkyl-, aryl-, and / or arylalkyl-modified silicones), such as SILTECH C-32 (available from Siltech Corporation), COATOSIL 1211C and 3573 (each available from Momentive), KF-410 (arylalkyl-modified polydimethylsiloxane) (available from Shin-Etsu Chemical Co., Ltd.), and BYK-322 and BYK-323 (arylalkyl-modified poly(dimethylsiloxane-co-methylalkylsiloxane)) (each available from BYK Additives & Instruments); - silicone acrylate copolymers, such as KP-541, KP-543, KP-545, KP-550 and KP-575 (acrylic polymers grafted with polydimethylsiloxane side chains, available from Shin-Etsu Chemical Co., Ltd.) and BYK-3550 (available from BYK Japan Co., Ltd.); - polyether-modified silicones, including those which are block copolymers with pendant graft structures formed from a linear or branched polydimethylsiloxane backbone containing one or more polyether side chains and optionally one or more fatty alkyl side chains as described above; - Fluoropolymers such as FC-4430 and FC-4432 available from 3M Corporation; - polyether-modified silicones, including those which are block copolymers having pendant graft structures formed from a linear or branched polydimethylsiloxane backbone containing one or more polyether side chains and optionally one or more fatty alkyl side chains, such as KF-6013 (PEG-9 dimethicone, uncapped, HLB=10.0), KF-6015 (PEG-3 dimethicone, uncapped, HLB=4.5), KF-6017 (PEG-10 dimethicone, uncapped, HLB=4.5), and KF-6038 (lauryl PEG-9 polydimethylsiloxyethyl dimethicone, uncapped, HLB=3.0), each available from Shin-Etsu Chemical Co., Ltd., and BYK-307 (polyether-modified polydimethylsiloxane) (available from BYK Additives & Instruments, as mentioned above); photocrosslinkable silicone acrylates or silicone polyether acrylates, such as TEGO RAD2100, TEGO RAD2200, TEGO RAD 2250, TEGO RAD2300 (silicone polyether acrylates) (each available from Evonik Industries), and BYK-UV3500 and 3530 (available from BYK); - polyacrylates, including polyacrylate copolymers and crosspolymers, such as BYK-381 and BYK-361N (polyacrylate copolymers) (each available from BYK), PEMULEN EZ-4U (acrylates / C10-C30 alkyl acrylate crosspolymer) and PEMULEN TR-2 (acrylic acid / C10-C30 alkyl acrylate crosspolymer) (each available from Lubrizol); - acetylenic diol and acetylenic glycol based gemini surfactants, such as SURFYNOL SEF and DYNOL surfactants (available from Evonik Industries); - polysiloxane-based gemini surfactants, such as TEGO TWIN 4100 (available from Evonik Industries); - non-ionic polyethers, such as substrate wetting surfactants, for example TEGO WET510 (hydrophilic polyether substrate wetting surfactant) (available from Evonik Industries); - amides or monoalkanolamides of fatty acids, including alkoxylated monoalkanolamides of fatty acids, such as coconut fatty acid monoethanolamide and coconut fatty acid monoethanolamide reacted with 2 to 20 moles of ethylene oxide; ethers, e.g., alkoxylated C1-C, including alkoxylated fatty alcohols 22 Alcohols, such as BIO-SOFT N-600 (C12-C13 alcohol ethoxylate), MAKON DA-4 (ethoxylated isodecyl alcohol), MERPOL SE (alcohol ethoxylate), and POLYSTEP TD-6 (ethoxylated tridecyl alcohol) (each available from Stepan), ethylene oxide / propylene oxide copolymers, alkoxylated alkylphenols, and alkyl polyglycosides (APGs) such as those made from the reaction of fatty alcohols with glucose; - fatty esters, such as ethoxylated and / or propoxylated fatty acids (for example, castor oil with 2 to 40 moles of ethylene oxide), alkoxylated glycerides (for example, PEG-24 glyceryl monostearate), glycol esters and derivatives, monoglycerides, polyglyceryl esters, esters of polyalcohols, and sorbitan / sorbitol esters, such as sorbitan monolaurate (for example, EMASOL L-10V, available from Kao Corporation) and polysorbates, including mono-, di- or tri-fatty acid esterified polysorbates, for example, TOXIMUL SEE-340 (sorbitan trioleate ethoxylate (20)) (available from Stepan); - glycosides of fatty alcohols, such as PLANTASENS NATURAL EMULSIFIER HE20 (cetearyl glucoside, sorbitan-olivate) (available from Clariant); sulfates, sulfonates, phosphates and phosphonates, such as alkyl sulfates, alkyl ester sulfates, alkyl ether sulfates, alkyl alkoxy ester sulfates, sulfated alkanolamides, glyceride sulfates, alkyl sulfonates, fatty alkyl benzene sulfonates, lower alkyl benzene sulfonates, alpha olefin sulfonates, lignosulfonates, alkyl aryl ether phosphates, alkyl ether phosphates, and phosphates of fatty alcohols or polyoxyalkylene ethers of fatty alcohols; and - fatty alkyl betaines, such as lauryl betaine (e.g., AMPHITOL 24B, available from Kao); Fatty alkylamidobetaines, for example, fatty amidopropyldimethylaminobetaine; Fatty alkyl sultaines, for example, fatty dimethylhydroxysultaine; Fatty alkylamidosultaines, for example, fatty amidopropyldimethylaminohydroxysultaine; Amine oxides, such as N-cocoamidopropyl dimethylamine oxide, Dimethyl fatty alkylamine oxides, such as dimethyl cocoamine oxide, lauryl dimethylamine oxide (e.g., AMPHITOL 20N, available from Kao); and imidazole-based amphoteric surfactants. amphoteric surfactants, including, but not limited to; - (e.g. ELEC AC available from Kao).

[0135] In some embodiments, the inkjet ink of the present disclosure is substantially free of silicone-containing surfactants. In some embodiments, the inkjet ink of the present disclosure is substantially free of polyether-containing surfactants. In some embodiments, the inkjet ink of the present disclosure is substantially free of such surfactants.

[0136] <(G) Additives> In addition to the components already mentioned, the inkjet ink may optionally contain various additives (G) to improve various ink properties and performance. For example, the inkjet ink may optionally contain technically appropriate levels of one or more anti-kogation agents, stabilizers, humectants, security taggants, or other inkjet ink additive(s) known to those skilled in the art.

[0137] The inkjet ink may optionally contain one or more opacifying agents, examples of which include, but are not limited to, titanium dioxide, zirconium silicate, zirconium oxide, tin oxide, cerium oxide, zinc oxide, aluminum oxide, silica, kaolin, calcium carbonate, magnesium carbonate, calcium magnesium carbonate, barium carbonate, sodium feldspar, potassium feldspar, nepheline, calcium silicate, mullite, wollastonite, and talc.

[0138] [Manufacturing method] Embodiments of the inkjet inks described herein may be prepared by any suitable method known to those skilled in the art. For example, (A) a terpene phenolic resin, (B) a solvent system including (B1) ethanol and (B2) a co-solvent, (C) an amine-modified silicone, and any desired optional ingredients (e.g., terpene resin, (E) colorant, (D) alkanolamine, (F) surfactant, and / or (G) additives) may be added in any order and stirred, agitated, and / or homogenized at a temperature between 20 and 100° C. for a suitable time to form a homogenous solution.

[0139] The resulting inkjet ink can then be loaded into a print cartridge, such as a FUNAI TIJ cartridge manufactured by Funai Manufacturing Co., Ltd., or other printhead suitable for ketone-based inks.

[0140] [Characteristics] The inkjet inks disclosed herein have an extended decap time. For example, decap time can be measured by printing a fine-line image (e.g., a barcode) (1 mm x 1 cm, fine lines, monochrome bitmap), exposing the inkjet ink to air for a specified time (e.g., 30 seconds, 1 minute, 10 minutes, 60 minutes, etc.), reprinting the same fine-line image, and comparing the decapped reprinted image with the original image to determine whether the fine-line image loses lines or loses clarity. If no lines lose lines or lose clarity during the tested time interval, the inkjet ink is given a "good" decap rating for that time interval. If one or two lines lose lines or lose clarity during the tested time interval, but not enough to significantly affect the clarity or readability of the fine-line image, the inkjet ink is given an "acceptable" decap rating for that time interval. If two or more lines lose lines or lose clarity during the tested time interval, the inkjet ink is classified as "poor" for that time interval. Suitable inkjet inks are those that can achieve an "acceptable" or "good" decap classification when decapped (i.e., exposed to air) for 30 seconds or more, preferably 1 minute or more, more preferably 10 minutes or more, even more preferably 30 minutes or more, and even more preferably 60 minutes or more.

[0141] The inkjet inks disclosed herein are also characterized by excellent adhesion to a variety of substrates. Adhesion is typically tested using a "peel tape test," in which adhesive tape, typically 3M Scotch® tape, is applied to the dried printed ink and then peeled off. Good ink adhesion is characterized by little ink removal from the substrate, i.e., little ink detectable on the adhesive tape, and / or no detectable change in the printed ink. An "acceptable" rating is characterized by a significant amount of ink removal from the substrate, i.e., ink visible on the adhesive tape, and / or noticeable changes in the printed ink (e.g., crosshatching or fading). A "poor" rating is characterized by a large amount of ink removal from the substrate, i.e., a large amount of ink visible on the adhesive tape (a replica of the print may be visible on the adhesive tape), and / or a significant reduction in print quality (e.g., crosshatching or fading).

[0142] The inkjet inks disclosed herein may be characterized by long running stability (also referred to as ink life or print life). To test the running stability of the inkjet ink, a fine-line image (e.g., a barcode) (1 mm x 1 cm, fine lines, monochrome bitmap) can be printed without interruption for a number of consecutive pages (e.g., 3,000 pages printed in a continuous printing run), and the print quality can be evaluated throughout the printing run by visually inspecting specific pages (e.g., page 1,000, page 2,000, and page 3,000) for missing nozzles. If no missing lines / loss of line sharpness occurs on the inspected page, the inkjet ink is assigned a running stability rating of "G" (good) for that page. If one or two lines are lost / lost in clarity on the inspected page, but not enough to significantly affect the clarity or readability of the fine line image, the inkjet ink is assigned a running stability rating of "A" (acceptable) for that page. If two or more lines are lost or lose sharpness on the inspected page, the inkjet ink is given a run stability rating of "NG" (poor) for the print. Inkjet inks that maintain a rating of "G" or "A", preferably a rating of "G", when printed for at least 100 pages, preferably at least 500 pages, preferably at least 1,000 pages, preferably at least 1,500 pages, preferably at least 2,000 pages, preferably at least 2,500 pages, preferably at least 3,000 pages, preferably at least 3,500 pages, preferably at least 4,000 pages, preferably at least 4,500 pages, preferably at least 5,000 pages are considered desirable from the standpoint of run stability (ability to remain dispersed / suspended without settling / settling or improper jetting).

[0143] [Printed material] The inkjet inks can be printed on a variety of substrates, including three-dimensional parts, as well as flat sheets or webs supplied in rolls, to produce a wide variety of printed articles. While flat substrates are suitable substrates for forming prints, a particular advantage of the present disclosure is that the disclosed inkjet inks can be used to form printed images on complex three-dimensional substrates, such as those with radiused, curved, sawtoothed, corrugated, fluted, lipped, and / or structured surfaces (e.g., grained surfaces). All of these are particularly challenging substrates because the ink must travel long distances to reach all parts of the complex surface. Printed articles may be suitable in the graphic arts, textile, packaging (e.g., food packaging, pharmaceutical packaging, etc.), lotteries, direct mail, business forms, and publishing industries, examples of which include tags or labels, lottery tickets, publications, packaging (e.g., food packaging, pharmaceutical packaging, blister packs, various other flexible packaging, etc.), folding cartons, rigid containers (e.g., plastic cups and tubs, glass containers, metal cans, bottles such as PET bottles, jars, tubes, etc.), envelopes, corrugated board, point-of-sale displays, etc. Particularly preferred printed materials are those having the dried form of inkjet ink disposed within complex three-dimensional features of the printed material, for example, those in which the printed image is disposed within the fluted or corrugated portions of a plastic container or the concave domed bottom of a metal can.

[0144] The inkjet inks can be printed onto porous (or permeable) substrates, examples of which include, but are not limited to, uncoated paper, wood, film, corrugated board (cardboard / fiberboard), and fabrics (including, but not limited to, woven fabrics, nonwoven fabrics, and foil-laminated fabrics).

[0145] The inkjet inks can also be printed on non-porous (or non-porous) substrates, including, but not limited to, various plastics, glass, metals (e.g., steel, aluminum, etc.), and / or non-porous papers (e.g., coated papers such as varnish-coated papers), molded plastic or metal parts, and flat sheets or rolls of plastic or metal films, such as polyesters (e.g., polyethylene terephthalate (PET)), biaxially oriented polystyrene (OPS), polyolefins (e.g., polyethylene (PE), polypropylene (PP), oriented polypropylene (OPP), biaxially oriented polypropylene (BOPP), polylactic acid (PLA), nylon and oriented nylon, polyvinyl chloride (PVC), cellulose triacetate (TAC), polycarbonate, acrylonitrile butadiene styrene (ABS), polyacetal, polyvinyl alcohol (PVA), coated papers (e.g., varnish-coated papers), and metals (e.g., steel, aluminum, etc.).

[0146] [Printing image formation method] In inkjet printing, a droplet-generating device called a printhead ejects precise dot patterns onto a print medium to form the desired printed image. The printhead has an array of precisely formed nozzles located on a nozzle plate and attached to an inkjet printhead substrate. The inkjet printhead substrate houses an array of firing chambers that receive inkjet ink in fluid communication with one or more ink reservoirs. Each firing chamber has a resistive element known as a fired resistor located opposite the nozzle so that inkjet ink collects between the fired resistor and the nozzle. Each resistor element is typically a pad of resistive material, measuring, for example, approximately 35 μm x 35 μm. The printhead is held and protected by a housing called a print cartridge or inkjet pen. When a particular resistor element is energized, a droplet of inkjet ink is expelled from the nozzle toward the print medium. The ejection of the ink droplets is typically under the control of a microprocessor, whose signals are transmitted by electrical traces to the resistor elements to form alphanumeric characters or other image patterns on the print medium. Because nozzle diameters are small, typically 10-40 μm, inks that minimize clogging are desirable. Thermal inkjet (TIJ) printing, in particular, has historically suffered from intermittent performance degradation during printing, where ink prematurely dries in and around the nozzles during decap time (print idle time), due to its open-to-air printhead design (the nozzle orifice is open to the atmosphere and does not have a valve seal at the orifice to allow ink pressurization).

[0147] The present disclosure provides a method for forming a printed image on a substrate by applying the inkjet ink of the present invention to the substrate with a thermal inkjet printhead and drying the inkjet ink. The use of the inkjet inks described herein overcomes the problem of short decap times (too fast solvent loss rates) commonly associated with thermal inkjet processes.

[0148] In some embodiments, the substrate is substantially free of amine-modified silicone. Such amine-modified silicone may be present on the surface of the substrate. In some printing methods or applications, the amine-modified silicone is applied to the substrate before applying the ink. Preferably, the methods described herein do not include applying an amine-modified silicone before applying the ink-jet ink. Preferably, in the methods described herein, the ink-jet ink is applied to a surface that is free of amine-modified silicone.

[0149] Any drop-on-demand printhead known to those skilled in the art of inkjet printing can be used as the printing unit in the present method, including continuous printheads, thermal printheads, electrostatic printheads, and acoustic printheads, preferably thermal printheads (with thermal transducers). Typical parameters, such as print resolution, print speed, printhead pulse warming temperature, drive voltage, and pulse length, can be adjusted depending on the printhead specifications. Printheads generally suitable for use in the methods herein have droplet sizes ranging from 2 to 80 pL and droplet frequencies ranging from 10 to 100 kHz. For example, high-quality prints can be obtained by setting the drive voltage at 8.0 to 9.5 volts, print speeds up to 300 feet per minute, pulse warming temperatures at 25 to 45°C, and pulse lengths at 0.7 to 2.5 microseconds. However, values ​​above or below these stated values ​​can also be used and still produce satisfactory prints. One non-limiting example of a printhead suitable for use in the disclosed method is the HP TIJ cartridge manufactured by HP.

[0150] After application, the inkjet ink is dried. In some embodiments, external heat can be applied to dry the applied inkjet ink, for example, by using a heater. However, it is preferred not to apply external heat to accelerate or increase the drying rate. Thus, in a preferred embodiment, drying is achieved by drying the applied inkjet ink under ambient conditions (in air, at about 23°C) for 30 seconds or less, preferably 25 seconds or less, more preferably 20 seconds or less, even more preferably 15 seconds or less, and even more preferably 10 seconds or less, without the use of an external heat source such as a heater. Furthermore, the methods of the present disclosure do not require energy curing (e.g., UV curing or electron beam curing). Once the applied ink is considered dry, a further coating of inkjet ink may be applied, or any processing steps known to those skilled in the art may be performed as desired.

[0151] It should also be appreciated that substrate surface treatments, such as corona treatment, atmospheric plasma treatment, and flame treatment, may optionally be employed in the methods herein prior to application of the inkjet ink to improve the properties of the printed matter, such as ink adhesion. The parameters of such substrate surface treatments can vary widely depending on the substrate material to be printed, the particular inkjet ink utilized, the printing method applied, and the desired properties and use of the printed matter.

[0152] The following examples are intended to further illustrate the ink-jet inks, but are not intended to limit the scope of the claims.

[0153] [Example] [material] DERTOPHENE T105 is a terpene phenolic resin (OHV = 20-60 mg KOH / g; SP = 105°C; Mw = approximately 700 g / mol) available from DRT / Pinova. Shin-Etsu KF865 is a side-chain monoamino-modified siloxane (viscosity at 25°C = 110 mmHg). 2 / s, specific gravity at 25°C = 0.97, refractive index at 25°C = 1.405, functional group equivalent = 5,000 g / mol), Shin-Etsu KF859 is a side-chain diamino-modified siloxane (viscosity at 25°C = 60 mm 2 / s, specific gravity at 25°C = 0.96, refractive index at 25°C = 1.403 (25°C), functional group equivalent = 6,000 g / mol), and Shin-Etsu KF6015 is a side-chain polyether-modified siloxane (viscosity at 25°C = 130 mm 2 / s, specific gravity at 25°C = 1.00, refractive index at 25°C = 1.419, hydrophilic lipophilic balance (HLB) = 4.5 to 5), and each is available from Shin-Etsu Silicones.

[0154] Valifast Black 3870 (also known as Solvent Black 29 or SB29) is a metal complex azo dye available from Orient Chemical Industry Co., Ltd. Valifast Red 3312 (also known as Solvent Red 122) is a metal complex azo dye available from Orient Chemical Industry Co., Ltd.

[0155] [Inkjet ink evaluation method] <Preparation of print sample> Inkjet ink examples were evaluated with HP TIJ cartridges manufactured by HP Corp. The inks were evaluated using HP thermal printing technology (software and hardware manufactured by Norwix, transport table manufactured by Kirk Rudy).

[0156] <Decap time evaluation> The following printing conditions were used to evaluate decap time: - Printing substrate: Plain paper (uncoated) - Print resolution: 300dpi x 300dpi (vertical x horizontal) - Voltage 8.6V - Pulse width 1.8μsec - Pulse humidification off - Print image: 100% duty (1mm x 1cm, monochrome bitmap, fine line image) (see Figure 2 for an example)

[0157] A fine-line image was printed and verified to ensure the printed image contained no missing or unclear lines (indicating clogged or missing nozzles). After verification, the printhead was left decapped for a set period of time (60 minutes) and then reprinted using the same fine-line image. The reprinted fine-line image (after the specified time period) was checked to determine whether any line loss / loss of line clarity occurred. If no line loss / loss of line clarity occurred, the inkjet ink was given a "good" decap rating for that time interval. If one or two lines were lost / lost in clarity during the tested time interval, but not enough to significantly affect the clarity or readability of the fine-line image during the tested time interval, the inkjet ink was given an "acceptable" decap rating for that time interval. If two or more lines were lost / lost in clarity during the tested time interval, the inkjet ink was classified as "poor" for that time interval. A suitable / desirable inkjet ink is one that achieves a decap classification of "acceptable" or "good" when decapped (ie, exposed to air) for each of the time intervals tested.

[0158] <Adhesion evaluation> The ink was printed onto LDPE film. One minute after printing, Scotch® Light Duty Packaging Tape 600 was applied to the ink with light pressure and quickly removed. The performance of the ink was rated according to the descriptions in Table 1 below.

[0159] [Table 1]

[0160] [Inkjet ink example] Examples of inkjet inks are shown in Tables 2A-2B. The amount of each component is expressed as % by weight based on the total weight of the inkjet ink (50 parts). * indicates a comparative example.

[0161] <Preparation method> To prepare the example inks, the resin, amino-modified silicone, and optional surfactant were first combined with the specified combination of ethanol and co-solvent and mixed with a mechanical stirrer for at least 30 minutes. The dye was then added to the mixture and mixed for at least 30 minutes to obtain the inkjet inks. The inkjet ink examples were then evaluated using HP TIJ cartridges manufactured by HP.

[0162] [Table 2A] [Table 2B]

[0163] [Inkjet ink performance] Table 3 shows that the combination of amine-modified silicone, ethanol, cosolvent, and terpene phenolic resin produced significant benefits in terms of decap time and adhesion (Examples 3, 4, 5, 7, 8, 9, 10, and 13). Conversely, inkjet inks without amino-modified silicone (Example 1) or cosolvent (Example 12) performed poorly in each test, resulting in results classified as "poor" for decap time and adhesion. When polyether-modified silicone (Example 6) was incorporated, decap time was adequate, but adhesion was unacceptable. Omission of ethanol (Example 11) or terpene phenolic resin (Example 15) resulted in good adhesion, but unacceptable decap time behavior.

[0164] With regard to the amount of co-solvent, loadings ranging from 4.5 to 15 parts (9 to 30 wt%) were found to provide acceptable or good decap behavior and acceptable or good adhesion on all substrates (see Examples 2, 3, 4, 5, 7, 8, 9, 10, 11, 13, 14, and 16).

[0165] [Table 3]

[0166] Where a numerical limit or range is stated, the endpoints are included, and all values ​​and subranges within the numerical limit or range are specifically included as if expressly written out.

[0167] As used herein, the words "a" and "an" and the like mean "one or more."

[0168] The present disclosure also contemplates other embodiments that "comprising," "consisting of," and "consisting essentially of" the embodiments or elements presented herein, whether explicitly stated or not.

[0169] Obviously, numerous modifications and variations of the present invention are possible in light of the above teachings. It is therefore to be understood that, within the scope of the appended claims, the invention may be practiced otherwise than as specifically described herein.

[0170] All patents and other references cited above are incorporated herein by this reference in their entirety, as if set forth at length.

Claims

1. (A) terpene phenol resin; (B) a solvent system comprising (B1) ethanol and (B2) a co-solvent; and (C) An inkjet ink containing an amine-modified silicone, The ink-jet ink, wherein the amine-modified silicone (C) comprises a silicone skeleton (main chain) and one or more organic amine side chains bonded to the silicone skeleton.

2. the terpene phenol resin (A) is a copolymer containing a monoterpene segment and a phenolic segment containing a phenolic compound, the phenolic segment is bonded to the monoterpene segment at at least one position selected from the group consisting of an ortho position relative to the phenolic hydroxyl group and a para position relative to the phenolic hydroxyl group; The ink-jet ink of claim 1.

3. the monoterpene segment is at least one bicyclic monoterpene selected from the group consisting of 3-carene, α-pinene, β-pinene, and camphene; The phenolic compound is phenol. The ink-jet ink of claim 2.

4. 2. The ink-jet ink according to claim 1, wherein the terpene phenol resin (A) has a hydroxyl value of 10 to 75 mgKOH / g.

5. 2. The ink-jet ink of claim 1, wherein the terpene phenolic resin (A) is present in an amount of 0.1 to 10 wt %, based on the total weight of the ink-jet ink.

6. 2. The ink-jet ink of claim 1, wherein the co-solvent (B2) is at least one selected from the group consisting of n-propanol, methyl ethyl ketone, ethyl acetate, propylene glycol monomethyl ether, and 1,3-dioxolane.

7. 2. The ink-jet ink of claim 1, wherein the weight ratio of (B1) ethanol to (B2) the co-solvent ((B1):(B2)) is from 1:1 to 25:

1.

8. 2. The ink-jet ink of claim 1, wherein the organic amine side chain is at least one selected from the group consisting of monoamines containing primary amines and diamines containing primary and secondary amines.

9. The viscosity of the amine-modified silicone (C) at 25°C is 25 to 250 mm 2 2. The ink-jet ink of claim 1, wherein the ink-jet ink is:

10. 2. The ink-jet ink of claim 1, wherein the amine-modified silicone has an amine functional group equivalent weight of 350 to 11,000 g / mol.

11. 2. The ink-jet ink of claim 1, wherein the amine-modified silicone is present in an amount of 0.1 to 10% by weight.

12. 10. The ink-jet ink of claim 1, which is substantially free of polyether-functionalized siloxanes.

13. 10. The ink-jet ink of claim 1, further comprising (D) an alkanolamine.

14. 14. The ink-jet ink of claim 13, wherein the alkanolamine (D) is present in an amount of 0.01 to 5 wt %, based on the total weight of the ink-jet ink.

15. 14. The ink-jet ink of claim 13, wherein the alkanolamine (D) is at least one selected from the group consisting of ethanolamine, propanolamine, isopropanolamine, diethanolamine, and triethanolamine.

16. The ink-jet ink of claim 1 , further comprising (E) a colorant.

17. The ink-jet ink of claim 16, wherein the colorant (E) is a metal complex azo dye.

18. A printed article comprising a substrate and the dried form of the ink-jet ink of claim 1 disposed on the substrate.

19. 1. A method of forming a printed image on a substrate, comprising: The method comprises applying the ink-jet ink of claim 1 onto the substrate using a thermal ink-jet printhead; and drying the inkjet ink; The method wherein the substrate is substantially free of amine-modified silicone.

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